Reaction products of nitroolefins and carbonyl compounds



United States Patent M 3,tl24',232 REACTION PRODUCTS 0F NITROOLEFINS ANDCARBONYL COMPOUNDS Edward B. Hodge, Terre Haute, Ind., assignor toCommercial Solvents Corporation, Terre Haute, Ind., acorporation ofMaryiand No Drawing. Filed Sept. 18, 1958, Ser. No. 761,671 1 Claim.(Cl. 260-444) My invention relates to the products of the reaction ofnitroolefins and carbonyl compounds and more particularly it relates tothe products of the reaction of nitroolefins and ketones or aldehydesand to the process of producing the same.

My new reaction products are obtained by the reaction of a nitroolefinhaving the structural formula Where R is selected from the groupconsisting of hydrogen, phenyl, furyl, halogen substituted phenyl, andlower alkyl substituted. phenyl; and R is selected from the groupconsisting of hydrogen, methyl, ethyl, propyl, and butyl with a carbonylcompound having the structural formula where R is selected from thegroup consisting of alkyl having up to carbon atoms, phenyl, halogensubstituted phenyl, lower alkyl substituted phenyl; and R is selectedfrom the groupconsisting of hydrogen and alkyl having up to 10 carbonatoms; and R and R together may be an alkylene radical having up to10'carbon atoms in the presence of a base, the mixture of reactantsbeing cooled during the reaction period to dissipate the heat ofreaction, and then acidified to obtain the product in the free formrather than in a salt form. The nitroolefins which I employ inmy-reaction can be substituted or unsubstituted. Among the substitutednitroolefins which I can employ are included Z-nitro-l-methyl-lpropene,Z-nitro-l-phenyl-l-propene, Z-nitro-l-p-chlorophenyl-l-propene,2-nitro-1-m-bromophenyl-l-propene, 2- nitro-l-p-tolyl-l-propene,2-nitro-l-(2,4-xylyl)-1-propene, Z-nitro-l-furyl-l-propene,2-nitro-l-p-ethylphenyl-l-propene, 2-nitro-1-phenyl-butene, etc.Unsubstituted nitroolefins which I can employ include nitroethene,2-nitro-lpropene, Z-nitro-l-butene, etc. The carbonyl compound which Iemploy in my reaction with the nitroolefin can be either an aldehyde ora ketone. Suitable carbonyl compounds include acetone, diethyl ketone,cyclohexanone, acetophenone, butyraldehyde, acetaldehyde, valeraldehyde,benzaldehyde, p-chlorobenzaldehyde, p-bromobenzaldehyde, etc. Asindicated the reaction is carried out in the presence of a base.Suitable bases include alkali metal and alkaline earth metal hydroxides.

I do not know the exact structure of theproduct of the reaction of anitroolefin and a carbonyl compound since there are at least twopossible products which could result. Without being limited by anyparticular theory, it is my belief that the products are eitheraci-nitrocarbonyl compounds or the hemiacetal of aci-nitrocarbonylcompounds. This belief is strengthened by the fact that infrared studiesof my compounds disclose that the strong bands indicating the presenceof nitro or ketone radicals are absent in my new compounds. The possiblereaction products which could be derived from the interaction of anitroolefin with a ketone is shown in the following generic equations:

By the process of Equation I the aci-nitrocarbonyl compound is formedand by the process of Equation II the hemiacetal of theaci-nitrocarbonyl compound is formed.

Alkali metal or alkaline earth metal salts are obtainedby reaction of anitroolefin and a carbonyl compound because the reaction is conducted inthe presence of a. base such as alkali metal oralkaline earth metalhydroxide. The desired nitrocarbonyl compound is obtained byacidification of the salt. Acids which I have found useful for thispurpose are acids commonly known as weak. acids." Such acids includeacetic acid, propionic The nitrocarbonyl compound can tion allequivalents obvious to those skilled in the art.

Example I To a solution of 32.6 grams of 2-nitro-1-phenyl-1- propene inml. of cyclohexanone was added a solution of18 grams of sodium hydroxidein 12 ml. of water. On stirring the mixture, a temperature rise occurredand the temperature was held at about 40 C. by intermittent cooling.After about 30 minutes, the reaction mixture was one phase and wasthereupon allowed to cool to room temperature after which it was pouredwith stirring into 400 ml. of 10% acetic acid. An oil formed which sooncrystallized, the crystals being then filtered and washed with acetoneto give 24 grams of white crystals having no definite melting point butdecomposing at 136-138 C. Analysis: Nitrogen, calculated (forl-phenyl-l-(Z-oxocyclohexyl)-2-aci-nitro-propane and correspondinghemiacetal)=5.36%, found=5.22%; carbon, calculated: 68.94%,found=69.l0%; hydrogen, calculated=7.35%, Found 7.49%. The product wasslightly soluble in acetone, methanol, ethyl acetate, nitromethane, andacetic acid. The product was dissolved in 5% sodium hydroxide from whichit was then precipitated by mixing with ether to obtain the sodium saltof the reaction product.

Example II An 81-gram portion of Z-nitro-l-phenyl-l-propene was mixedwith 25 ml. of butyraldehyde and to the mixture was then added asolution of 2-grams of sodium hydroxide in 5 ml. of mater. The resultingmixture was stirred and when a temperature rise occurred, thetemperature was held at about 4045 C. by intermittent cooling. Uponcompletion of the reaction, a thick yellow oil was obtained as theproduct.

Example III A 17.7-gram portion of 2-nitro-l-p-tolyl-l-propene was mixedwith 60 ml. of cyclohexanone and to the resulting Patented Mar. 6, 162

Example IV A 15.3-gram portion of 2-nitro-1-(2-furyl)-1- propene wasmixed with 40 mil. of cyclohexanone and to the resulting mixture asolution of 4 grams of sodium hydroxide in 6 ml. of water was added. Theresulting mixture was stirred for 20 minutes with cooling to maintain atemperature of about 4045 C. after which the reaction mixture was pouredinto 200 ml. of 10% acetic acid. The acetic acid mixture was stirred forabout 3 minutes, filtered,

and the precipitate washed with acetone to obtain 8 grams of product.

Example V A ZO-gram portion of Z-nitro-l-phenyl-l-propene was mixed with100 m1. of acetone and to the mixture was added a solution of 4 grams ofsodium hydroxide in 7 ml. of water. The resulting mixture was stirredand intermittently cooled to maintain a temperature of about 40-45 C.Upon completion of the reaction, the mixture was cooled to 20 C. andpoured into 200 ml. of 10% acetic acid. A soft white solid productprecipitated which was thereupon removed by filtration.

My new compounds are useful as intermediates in the formation ofinsecticidal materials. For example, the bromine derivatives of my newreaction products have been found effective against pea aphids. Thefollowing example is offered to illustrate the preparation of brominederivatives of my new compositions.

Example VI To 75 ml. of methanol was added a solution of 1 g. of sodiumhydroxide in ml. water. To this solution was added 7.5 g. of thereaction product of 2-nitro-l-pchlorophenyl-l-propene and cyclohexanoneand after almost complete solution, the mixture was filtered. A solutionof 1.4 ml. of bromine in 25 ml. of methanol was then added dropwise withstirring at 10 C. until 20 ml. had been added and a yellow colorobtained. A 5 ml. portion of water was then added and the mixture cooledto crystallize the product. The product was filtered, washed with 25 ml.of methanol and 5 ml. of water to give 3.9 g. of product. The productwas recrystallized from cyclohexane to give 1.9 g. having a meltingpoint of 114-1 15 C. Analysis: Calculated, N=3.74%, Br=21.65%, Cl=9.46%,found, N=3.65% Br=2l.39%, Cl=9.50%.

The bromine derivative of the reaction product of 2-nitro-l-p-chlorophenyl-l-propene and cyclohexanone obtained as describedin Example VI gave a kill of pea aphids at a concentration of 1% as anemulsified solution in water.

This application is a continuation-in-part of my copending applicationSerial No. 547,049, now abandoned, filed November 15, 1955.

Now having described my invention what I claim is:

As a composition of matter, a compound produced by a process whichconsists essentially of reacting a nitroolefin having the formula:

R-CH=CRX where R is selected from the group consisting of phenyl,monohalo-substituted phenyl, monoalkyl-substituted phenyl,dialkyl-substituted phenyl, and lower alkyl and R is selected from thegroup consisting of hydrogen and lower alkyl with a carbonyl compoundhaving the formula:

References Cited in the file of this patent UNITED STATES PATENTS2,343,256 Hass Mar. 7, 1944 UNITED STATES PATENT OFFICE CERTIFICATE OFCORRECTION March 6 1962 Patent No. 3,02%232 Edward B.. Hodge It ishereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 2 line 64 for 'mater" read water column 3 line l4! for "40 mil.read 40 ml,

Signed and sealed this 28th day of August 1962.

(SEAL) Attest:

ESTON G, JOHNSON DAVID L. LADD Attesting Officer Commissioner of Patents

